Calcium Effects in the DOE Surfactant-Polymer Pilot Test
Abstract: The surfactant and polymer slugs for the chemical recovery pilot test operated by DOE were designed to be effective at the divalent ion concentration of the injection water. Laboratory tests indicated that even if there were no intrusion by the formation brine, the slugs would experience an increase in divalent ion content on contact with the rock. It was found that with calcium present, optimal salinity of the surfactant system was reduced by 4 to 7 times the amount of calcium on an equivalent basis. The mini… Show more
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Cited by 4 publications
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Background. For chemical flooding formulations, optimal salinity changes with overall surfactant concentration when the phase behavior is observed in test tubes. Applying these observations to the mathematical simulator is questionable because chromatographic mechanisms during displacement through porous media result in different compositions. Purpose. This work sought the mechanism for the observed change so that calculated optimal salinity can be expressed through the appropriate intensive variable rather than overall surfactant concentration. Method. Association of the alcohol has been described by partition coefficients for distribution of the alcohol among brine, oil, and surfactant. The alcohol was isopropanol (IPA), 1-butanol (NBA), or tertiary amyl alcohol (TAA) in the systems in which they were included and was used to represent a disulfonate in the system with Petrostep petroleum sulfonate. Association of sodium and divalent ions with surfactant has been described by the Donnan equilibrium model, which experimental observations show can be applied to microemulsions as well as to micelles. Conclusions. For the seven systems investigated, the change in optimal salinity is a function of (1) the alcohol associated with the surfactant and (2) the divalent ion fraction of the associated counterions. Introduction Reed and Healy reviewed the concept of optimal salinity for minimum inter-facial tension (IFT) and its relationship to phase behavior. They showed that, as a first approximation, phase behavior can be represented by electrolyte concentration and three pseudocomponents: brine, oil, and surfactant plus cosolvent. If the system actually contains three components plus sodium chloride, optimal salinity should be independent of overall surfactant concentration and WOR. However. in the system Reed and Healy investigated, optimal salinity changed with overall surfactant concentration and WOR, which indicates that the system did not contain just sodium chloride plus three additional components. To handle this problem, Vinatieri and Fleming suggested using regression analysis to determine the best set of pseudocomponents. Then alcohol can be included with the oil and brine as pseudocomponents. Blevins et al. examined the phase behavior of a quaternary system (with brine as a pseudocomponent) by examining pseudoternary planes on a quaternary diagram. Glover et al. showed that the change in optimal salinity of a system containing divalent ions can be modeled by (1) considering the equilibrium composition of the brine, and (2) describing optimal salinity as a linear function of the concentration of divalent ions associated with the sulfonate. They assumed that NEODOL 25-3S did not associate divalent ions. (NEODOL 25-3S is a sodium salt of C12-C15 alkyl ether sulfate, with an average ethylene oxide number of three. Hereafter in this paper it is abbreviated as N253S.) Pope and Nelson showed that phase behavior and IFT's can be modeled in a compositional simulator when optimal salinity and the upper and lower limits of the Type III environment are known. The purpose of this work is to model alcohol or multiple surfactant components and divalent ions so that they can be included in a compositional simulator. Thermodynamic Analysis The Gibbs phase rule is used to show that a four-component system of pure oil, surfactant, water, and NaCl has an optimal salinity that does not depend on overall surfactant concentration. SPEJ P. 971^
Background. For chemical flooding formulations, optimal salinity changes with overall surfactant concentration when the phase behavior is observed in test tubes. Applying these observations to the mathematical simulator is questionable because chromatographic mechanisms during displacement through porous media result in different compositions. Purpose. This work sought the mechanism for the observed change so that calculated optimal salinity can be expressed through the appropriate intensive variable rather than overall surfactant concentration. Method. Association of the alcohol has been described by partition coefficients for distribution of the alcohol among brine, oil, and surfactant. The alcohol was isopropanol (IPA), 1-butanol (NBA), or tertiary amyl alcohol (TAA) in the systems in which they were included and was used to represent a disulfonate in the system with Petrostep petroleum sulfonate. Association of sodium and divalent ions with surfactant has been described by the Donnan equilibrium model, which experimental observations show can be applied to microemulsions as well as to micelles. Conclusions. For the seven systems investigated, the change in optimal salinity is a function of (1) the alcohol associated with the surfactant and (2) the divalent ion fraction of the associated counterions. Introduction Reed and Healy reviewed the concept of optimal salinity for minimum inter-facial tension (IFT) and its relationship to phase behavior. They showed that, as a first approximation, phase behavior can be represented by electrolyte concentration and three pseudocomponents: brine, oil, and surfactant plus cosolvent. If the system actually contains three components plus sodium chloride, optimal salinity should be independent of overall surfactant concentration and WOR. However. in the system Reed and Healy investigated, optimal salinity changed with overall surfactant concentration and WOR, which indicates that the system did not contain just sodium chloride plus three additional components. To handle this problem, Vinatieri and Fleming suggested using regression analysis to determine the best set of pseudocomponents. Then alcohol can be included with the oil and brine as pseudocomponents. Blevins et al. examined the phase behavior of a quaternary system (with brine as a pseudocomponent) by examining pseudoternary planes on a quaternary diagram. Glover et al. showed that the change in optimal salinity of a system containing divalent ions can be modeled by (1) considering the equilibrium composition of the brine, and (2) describing optimal salinity as a linear function of the concentration of divalent ions associated with the sulfonate. They assumed that NEODOL 25-3S did not associate divalent ions. (NEODOL 25-3S is a sodium salt of C12-C15 alkyl ether sulfate, with an average ethylene oxide number of three. Hereafter in this paper it is abbreviated as N253S.) Pope and Nelson showed that phase behavior and IFT's can be modeled in a compositional simulator when optimal salinity and the upper and lower limits of the Type III environment are known. The purpose of this work is to model alcohol or multiple surfactant components and divalent ions so that they can be included in a compositional simulator. Thermodynamic Analysis The Gibbs phase rule is used to show that a four-component system of pure oil, surfactant, water, and NaCl has an optimal salinity that does not depend on overall surfactant concentration. SPEJ P. 971^
The oil-recovery effectiveness of a chemical flood has been proved related to the phase behavior of the brine/oil/surfactant system. In particular, it is advantageous to formulate the system so that optimal threephase behavior is obtained. However, it also has been demonstrated that all the optimized systems are not equivalent in terms of solubilization. interfacial tensions (IFT's), and oil-recovery efficiency. This paper addresses the conditions that promote high solubilization in microemulsions, a property correlated to the values of the IFT and therefore correlated to the ability of such systems to displace the oil in porous media. When one formulation parameter is changed, another parameter must be varied at the same time for compensation to reoptimize the system. The mechanism of solubilization is investigated experimentally by considering the usual formulation parameters: salinity, oil type, alcohol type and concentration, and surfactant structure and type (anionics and nonionics). The results are interpreted in terms of interaction energies between surfactant, oil, and water. In particular, the role of the alcohol and its impact on the solubilization by amphiphilic systems are discussed in detail and interpreted. Moreover, the concepts developed in this paper explain the effect of the surfactant structure and therefore aid in the design of amphiphilic molecules exhibiting a high solubilizing power for given conditions of brine, temperature, etc. Introduction Mobilization and transport of residual oil by chemical-flooding processes involve various mechanisms that must be considered when formulating a surfactant slug, but, among them, it is well known that IFT's between phases play a major role. Reed and Healy have shown phases play a major role. Reed and Healy have shown that ultralow IFT's can be attained when a microemulsion phase (surfactant-rich phase, the so-called "middle phase (surfactant-rich phase, the so-called "middle phase") is in equilibrium simultaneously with an oil phase") is in equilibrium simultaneously with an oil phase and a water phase. They first have defined the phase and a water phase. They first have defined the concept of optimal salinity as being the point where the IFT's at the oil-middle phase and middle phase/water interfaces are equal. At that point, the volumes of oil and water solubilized in the middle phase generally are identical, although there is no theoretical basis for that. A correlation between the values of the quantities of oil and water solubilized in the middle phase and the values of the IFT's between the phases also has been found: the lower the tension, the higher the solubilization. Therefore, it appears judicious to start the screening procedure of surfactant systems for enhanced oil procedure of surfactant systems for enhanced oil recovery (EOR) by looking for the point where equal volumes of oil and water are solubilized in the surfactant phase of a three-phase system. During recent years, phase of a three-phase system. During recent years, much time has been devoted to discovering that point, and the rules for compensating changes in the formulation variables have been established for anionic and non-ionic surfactants. We must emphasize that, if we start from an optimized system and we change a formulation variable defining the system, the optimal state is lost, and another formulation variable must be changed to reach a new optimal state. All optimized systems are not equivalent, as shown in previous results, and consideration of the amount of previous results, and consideration of the amount of oil and water solubilized in such systems provides a criterion to compare them. In a previous paper, we carried out a systematic study of the effect of the formulation variables on the solubilization at optimum by anionic surfactants. Some results concerning nonionics have been presented recently presented recently. SPEJ p. 327
Members SPE-AIME "Retired. Formerly with U.S. DOE. This paper was presented at the SPE/DOE Fourth Symfmsium on Enhanced Oil Recovery held in Tulsa, OK, April 15-18, 1S64. The material is subject to correction by the author. Permission to copy is restricted to an abstract of not more than 3DD words. Write SPE, 6200 North Central Expressway, Draww 64706, Dallas, Texas 75206 USA. Telex 730969 SPEDAL. kBS'TMCT of three petroleum sulfonates, with a built-in cosurfactant that was primarily amyl and ethoxylated hexylResults are presented from three areaa of the alcohola. Its phase behavior with Delaware-Childers laboratory studies in connection with the surfactant-crude was classical Winsor (~)with an optimal salinity polymer pilot field teat conducted by the U. S. Depart-of 1.3% NaC1. The surfactant slug was injected at the nent of Bnergy: 1. Sulfonate produced, both in the suboptimal ealinity 0.8% NaC1. The polymer was Nalco Eield and laboratory tests, was chiefly in the oil Chemical Co. Nal-flo B, a polyacrylamide 30% anionic phase, indicating a marked departure from the optimal and said to have an average molecular weight 8-10 :ondition of equal distribution. This cannot be attri-inillion. The mobility buffer slug hae a salinity of buted to increased salinity, as the salinity of the 2.29% NaCl, and was graded in eight logarithmic stepe produced brine waa not very different from that of the ranging from 20cp (SaPa.s)to 0.8 cp (mPa.s) (water at Lnjectedsurfactant slug. Suggeeted causes are dilu-reeervoir temperature). The laboratory parametric tion and changing waterfoil ratio that resulted in study presented here and previously Q) was carried out Fractional repartitioning of the complex alcohol and on an outdated polymer sample having about 80% of its sulfonate.original viscoeity. Therefore the values reported 2.The use of dilute brine instead of fresh water for should be considered on a relative basic only. the polymer slug avoided large variations in viscosity that would have resulted from eeaeonal variations in EXPERIMENTAL PROCEDURES the supply water. In this connection, it was found that the non-Newtonian character of the polymer wae Flood tests iifferent for two solutions at the same viscosity but Cores were vacuum-saturated with synthetic proiifferent polynter/saltcomposition. duced brine, mounted in a Hassler holder with confining 3.Berea cores, when fired, behaved like the oil-wet preseure of 180-400 psi (1.2-2.8 MPa), oil flooded to reservoir coree in respect to oil recovery, relative irreducible water, and then flooded at 1-6 ftfda (0.3-2 permeability, and flow-resistance history. A supple-n/da) with 0.88% NaCl, to residual oil. Chemical nentary eilicone treatment to give the same nettability flooding, at 1-2 ft/da (0.3-0.6 m/da) consisted of IS the oilfield cores had no beneficial effect. sequentially injecting 0.
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